UV-photostabilized sunscreen compositions comprising dibenzoylmethane/benzophenone compounds

ABSTRACT

Topically applicable cosmetic/dermatological sunscreen compositions well suited for the stable UV-photoprotection of human skin and/or hair are devoid of any p-methylbenzylidenecamphor, but contain (a) an effective photoprotecting amount of at least one UV-screening dibenzoylmethane compound, and (b) an effective photostabilizing amount of at least on UV-screening amino-substituted 2-hydroxybenzophenone compound having the following structural formula (I):  
                 
 
     formulated into (c) a topically applicable, cosmetically/dermatologically acceptable vehicle, diluent or carrier therefor.

CROSS-REFERENCE TO PRIORITY APPLICATION

[0001] This application claims priority under 35 U.S.C. § 119 ofFR-01/15858, filed Dec. 7, 2001, hereby expressly incorporated byreference.

BACKGROUND OF THE INVENTION

[0002] 1. Technical Field of the Invention

[0003] The invention relates to a cosmetic or dermatological compositionfor topical use, characterized in that it comprises, in a cosmeticallyacceptable vehicle:

[0004] (a) at least one UV screening agent of the dibenzoylmethanederivative type and

[0005] (b) at least one specific amino-substituted 2-hydroxybenzophenonederivative; the said composition not comprisingp-methylbenzylidenecamphor.

[0006] The invention also relates to a process for improving thestability with respect to UV radiation of at least one dibenzoylmethanederivative present in a cosmetic or dermatological composition notcomprising p-methylbenzylidenecamphor which consists in combining, withthe said dibenzoylmethane derivatives, an effective amount of at leastone specific amino-substituted 2-hydroxybenzophenone derivative.

[0007] 2. Description of the Prior Art

[0008] It is known that light radiation with wavelengths of between 280nm and 400 nm makes possible browning of the human epidermis and thatrays with wavelengths more particularly of between 280 and 320 nm, knownunder the name of UV-B, cause erythemas and skin burns which may beharmful to the development of natural tanning. For these reasons and foraesthetic reasons, there exists a continual demand for means forcontrolling this natural tanning, for the purpose of thus controllingthe color of the skin; it is thus advisable to screen out this UV-Bradiation.

[0009] It is also known that UV-A rays, with wavelengths of between 320and 400 nm, which cause browning of the skin, are capable of bringingabout a detrimental change in the latter, in particular in the case ofsensitive skin or of skin continually exposed to solar radiation. UV-Arays cause in particular a loss in the elasticity of the skin and theappearance of wrinkles, resulting in premature aging of the skin. Theypromote the triggering of the erythemal reaction or accentuate thisreaction in some subjects and can even be the cause of phototoxic orphotoallergic reactions. Thus, for aesthetic and cosmetic reason, suchpreservation of the natural elasticitiy of the skin, for example, moreand more people with to control the effect of UV-A radiation on theirskin. It is therefore desirable also to screen out UV-radiation.

[0010] In this respect, a particular advantageous family of UV-Ascreening agents is currently composed of dibenzoylmethane derivativesand in particular 4-tert-butyl-4′-methoxydibenzoylmethane; this isbecause derivatives exhibit a high intrinsic absorbance. Thesedibenzoylmethane derivatives, which are now products well known per seas screening agents active in the UV-A region, are disclosed inparticular in French Patent Applications FR-A-2 326 405 and FR-A-2 440933 and in European Patent Application EP-A-0 114 607; furthermore,4-tert-butyl-4′-methoxydibenzoylmethane is currently offered for saleunder the trademark of “Parsol 1789” by Hoffmann-LaRoche.

[0011] Unfortunately, it is found that dibenzoylmethane derivatives areproducts which are relatively sensitive to ultraviolet radiation (inparticular UV-A radiation), that is to say, more specifically, that theyhave an unfortunate tendency to decompose more or less rapidly under theeffect of the latter. Thus, this substantial lack of photochemicalstability of dibenzoylmethane derivatives in the face of ultravioletradiation, to which they are naturally intended to be subjected, doesnot make it possible to guarantee constant protection during prolongedexposure to the sun, so that repeated applications at regular andfrequent intervals have to be carried out by the user in order to obtaineffective protection of the skin against UV radiation.

[0012] The photostabilization of dibenzoylmethane derivatives withrespect to UV radiation constitutes, to date, a problem which has notyet been solved in a completely satisfactory manner.

[0013] Antisun compositions formed from amino-substituted2-hydroxybenzophenone derivatives which can comprise other additionalscreening agents, such as dibenzoylmethane derivatives, in the presenceof p-methylbenzylidenecamphor, are known in Patent Applications DE 10012 408 and EP-A-1 046 391.

SUMMARY OF THE INVENTION

[0014] In point of fact, the Applicant company has now just discovered,surprisingly, that, by combining the abovementioned dibenzoylmethanederivatives with an amount of at least one specific amino-substituted2-hydroxybenzophenone derivative, it is possible to improve,substantially and notably, the photochemical stability (orphotostability) of these same dibenzoylmethane derivatives.

[0015] Thus, in accordance with one of the subject-matters of thepresent invention, a novel cosmetic or dermatological composition fortopical use is now provided, which composition is characterized in thatit comprises, in a cosmetically acceptable vehicle:

[0016] (a) at least one UV screening agent of the dibenzoylmethanederivative type and

[0017] (b) at least one specific amino-substituted 2-hydroxybenzophenonederivative of formula (I) which will be defined later; the saidcomposition not comprising p-methylbenzylidenecamphor.

[0018] The invention also relates to a process for improving thestability with respect to UV radiation of at least one dibenzoylmethanederivative in a cosmetic or dermatological composition not comprisingp-methylbenzylidenecamphor which consists in combining, with the saiddibenzoylmethane derivative, an effective amount of at least onespecific amino-substituted 2-hydroxybenzophenone derivative.

[0019] The term “effective amount of amino-substituted2-hydroxybenzophenone derivative” in accordance with the invention isunderstood to mean an amount sufficient to produce a noteworthy andsignificant improvement in the photostability of the dibenzoylmethanederivative or derivatives of the photoprotective cosmetic composition.This minimum amount of photostabilizing agent to be employed, which canvary depending on the nature of the cosmetically acceptable vehicle usedfor the composition, can be determined without any difficulty by meansof a conventional test for measuring photostability.

[0020] Finally, another subject-matter of the present invention is theuse of an amino-substituted 2-hydroxybenzophenone derivative of formula(I) in the preparation of a cosmetic or dermatological compositioncomprising at least one dibenzoylmethane derivative and not comprisingp-methylbenzylidenecamphor for the purposed of improving the stabilitywith respect to UV radiation of the said dibenzoylmethane derivativepresent.

[0021] Other characteristics, aspects and advantages of the presentinvention will become apparent on reading the detailed description whichwill follow.

DETAILED DESCRIPTION OF BEST MODE AND SPECIFIC/PREFERRED EMBODIMENTS OFTHE INVENTION

[0022] The ratio by weight of the amino-substituted2-hydroxybenzophenone derivative to the dibenzoylmethane derivative ispreferably greater than 1.

[0023] The amino-substituted 2-hydroxybenzophenone derivatives inaccordance with the invention correspond to the following formula (I):

[0024] in which:

[0025] R¹ and R², which may be identical or different, denote a hydrogenatom, a C₁-C₂₀ alkyl radical, a C₂-C₁₀ alkenyl radical, a C₃-C₁₀cycloalkyl radical or a C₃-C₁₀ cycloalkenyl radical;

[0026] R¹ and R² can also form, with the nitrogen atom with which theyare bonded, a 5- or 6-membered heterocyclic ring member;

[0027] R³ and R⁴, which may be identical or different, denote a C₁-C₂₀alkyl radical, a C₂-C₁₀ alkenyl radical, a C₃-C₁₀ cycloalkyl radical, aC₃-C₁₀ cycloalkenyl radical, a C₁-C₁₂ alkoxy radical, a(₁-C₂₀)alkoxycarbonyl radical, a C₁-C₁₂ alkylamino radical, adi(C₁,₁₂)alkylamino radical, an aryl radical or a heteroaryl which isoptionally substituted, or a water-solubilizing substituent chosen froma carboxylate group, a sulphonate group or an ammonium residue;

[0028] X denotes a hydrogen atom or a COOR⁵ or CONR⁶R⁷ group;

[0029] R⁵, R⁶ and R⁷, which may be identical or different, denote ahydrogen atom, a C₁-C₂₀ alkyl radical, a C₂-C₁₀ alkenyl radical, aC₃-C₁₀ cycloalkyl radical, a C₃-C₁₀ cycloalkenyl radical, a —(YO))₀-Zgroup or an aryl group;

[0030] Y denotes —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄- or —CH-(CH₃)-CH₂—;

[0031] Z represents —CH₂—CH₃, —CH₂CH₂CH₃, —CH₂—CH₂—CH₂—CH₃ or—CH(CH₃)-CH₃;

[0032] m is an integer varying from 0 to 3;

[0033] n is an integer varying from 0 to 3;

[0034] o is an integer varying from 1 to 2.

[0035] Mention may be made, as C₁-C₂₀ alkyl radicals, of, for example:methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethyl-ethyl, n-pentyl, 1-methylbutyl,2-methylbutyl, 3-methyl-butyl, 2,2-dimethylpropyl, 1-ethylpropyl,n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl,n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,n-nonadecyl or n-icosyl.

[0036] Mention may be made, as C₂-C₁₀ alkenyl groups, of, for example:vinyl, n-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl,2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl,1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl.

[0037] Mention may be made, as C₁-C₁₂ alkoxy radicals, of: methoxy,ethoxy, n-propoxy, n-butoxy, n-pentoxy, 1-methylpropoxy, 3-methylbutoxy,2,2-dimethylpropoxy, 1-methyl-1-ethylpropoxy, octoxy, 2-methylpropoxy,1,1-dimethylpropoxy, hexoxy, heptoxy or 2-ethylhexoxy.

[0038] Mention may be made, as C₃-C₁₀ cycloalkyl radicals, of, forexample: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,1-methylcyclo-propyl, 1-ethylcyclopropyl, 1-propylcyclopropyl,1-butylcyclopropyl, 1-pentylcyclopropyl, 1-methyl-1-butylcyclopropyl,1,2-dimethylcyclopropyl, 1-methyl-2-ethylcyclopropyl, cyclooctyl,cyclononyl or cyclodecyl.

[0039] Mention may be made, as C₃-C₁₀ cycloalkenyl radicals having oneor more double bonds, of: cyclopropenyl, cyclobutenyl, cyclopentenyl,cyclopentadienyl, cyclohexenyl, 1,3-cyclohexadienyl,1,4-cyclohexadienyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl,1,5-cyclooctadienyl, cyclooctatetraenyl, cyclononenyl or cyclodecenyl.

[0040] The cycloalkyl or cycloalkenyl radicals can comprise one or moresubstituents (preferably from 1 to 3) chosen, for example, from halogen,such as chlorine, fluorine or bromine; cyano; nitro; amino; C₁-C₄alkylamino; di(C₁-C₄)alkylamino; C₁-C₄ alkyl; C₁-C₄ alkoxy; or hydroxyl.They can also comprise from 1 to 3 heteroatoms, such as sulphur, oxygenor nitrogen, the free valencies of which can be occupied by a hydrogenor a C₁-C₄ alkyl radical.

[0041] The aryl groups are preferably chosen from phenyl or naphthylrings which can comprise one or more substituents (preferably from 1 to3) chosen, for example, from halogen, such as chlorine, fluorine orbromine; cyano; nitro; amino; C₁-C₄ alkylamino; di(C₁l-C₄)alkylamino;C₁-C₄ alkyl; C₁-C₄ alkoxy; or hydroxyl. Preference is more particularlygiven to phenyl, methoxyphenyl and naphthyl.

[0042] The heteroaryl groups generally comprise one or more heteroatomschosen from sulphur, oxygen or nitrogen.

[0043] The water-solubilizing groups are, for example, carboxylate orsulphonate groups and more particularly their salts with physiologicallyacceptable cations, such as alkali metal salts or trialkylammoniumsalts, such as tri(hydroxyalkyl)-ammonium or2-methylpropan-1-ol-2-ammonium salts. Mention may also be made ofammonium groups, such as alkylammoniums, and their salified forms withphysiologically acceptable anions.

[0044] Mention may in particular be made, as examples of the 5- or6-membered heterocyclic ring member; formed by the R¹ and R² radicalswith the nitrogen atom, of pyrrolidine or piperidine.

[0045] The amino groups can be attached to the benzene ring in theortho, meta or para position with respect to the carbonyl radical andmore preferably in the para position.

[0046] A family of preferred compounds of formula (I) comprises thosechosen from those of following formula (Ia):

[0047] in which:

[0048] R¹ and R², which may be identical or different, denote a hydrogenatom or a C₁-C₁₂ alkyl radical or form, with the nitrogen atom withwhich they are bonded, a 5- or 6-membered heterocyclic ring member;

[0049] X denotes COOR⁵ or CONR⁶R⁷;

[0050] R⁵ denotes a hydrogen atom, a C₁-C₁₂ alkyl radical or a C₃-C₆cycloalkyl radical;

[0051] R⁶ and R⁷, which may be identical or different, denote a hydrogenatom, a C₁-C₁₂ alkyl radical or a C₅-C₆ cycloalkyl radical.

[0052] The more particularly preferred compounds of formula (Ia) arethose for which:

[0053] R¹ and R², which may be identical or different, denote a C₁-C₄alkyl radical and more particularly ethyl;

[0054] R⁵ denotes a C₃-C₈ alkyl radical;

[0055] R⁶ and R⁷, which may be identical or different, denote a C₁-C₈alkyl radical.

[0056] Another family of preferred compounds of formula (I) comprisesthose chosen from those of following formula (Ib):

[0057] in which:

[0058] R¹ and R², which may be identical or different, denote a C₁-C₂alkyl radical or form, with the nitrogen atom with which they arebonded, a 5- or 6-membered heterocyclic ring member;.

[0059] Mention may more particularly be made, among the compounds offormula (Ib), of:

[0060] 4-diethylamino-2-hydroxyphenyl phenyl ketone,

[0061] 4-pyrrolidino-2-hydroxyphenyl phenyl ketone.

[0062] A family of more particularly preferred compounds of formula (I)comprises those chosen from those of following formula (Ic):

[0063] in which:

[0064] R¹ and R², which may be identical or different, denote a hydrogenatom or a C₁-C₈ alkyl radical or form, with the nitrogen atom with whichthey are bonded, a 5- or 6-membered heterocyclic ring member;

[0065] R⁵ denotes a hydrogen atom, a C₁-C₁₂ alkyl radical or a C₃-C₆cycloalkyl radical.

[0066] Mention may be made, among the compounds of formula (Ic), of:

[0067] 2-(4-pyrrolidino-2-hydroxybenzoyl)benzoate

[0068] methyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate

[0069] 2-ethylhexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate

[0070] cyclohexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate

[0071] n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate

[0072] [lacuna] 2-(4-dibutylamino-2-hydroxybenzoyl)benzoate

[0073] methyl 2-(4-dibutylamino-2-hydroxybenzoyl)benzoate

[0074] isobutyl 2-(4-dibutylamino-2-hydroxybenzoyl)benzoate.

[0075] A very particularly preferred compound of formula (I) is n-hexyl2-(4-diethylamino-2-hydroxy-benzoyl) benzoate.

[0076] The compounds of formula (I) as defined above are known per seand their structures and their syntheses are disclosed in PatentApplications EP-A-1 046 391 and DE 100 12 408 (which form an integralpart of the content of the description).

[0077] The amino-substituted 2-hydroxybenzophenone derivatives inaccordance with the invention are preferably present in the compositionof the invention in proportions preferably ranging from 0.1 to 15% byweight and more preferably from 1 to 10% by weight and more particularlyfrom 2 to 8% by weight with respect to the total weight of thecomposition.

[0078] As indicated above, the dibenzoylmethane derivatives intended tobe photostabilized in the context of the present invention are productswhich are already well known per se and which are disclosed inparticular in the abovementioned documents FR 2 326 405, FR 2 440 933and EP 0 114 607, the teachings of which documents are, insofar as theyaffect the actual definition of these products, entirely included by wayof references in the present description.

[0079] According to the present invention, it is possible, of course, toemploy one or more dibenzoylmethane derivatives.

[0080] Mention may in particular be made, among dibenzoylmethanederivatives coming particularly well within the scope of the presentinvention, of, without limitation:

[0081] 2-methyldibenzoylmethane,

[0082] 4-methyldibenzoylmethane,

[0083] 4-isopropyldibenzoylmethane,

[0084] 4-tert-butyldibenzoylmethane,

[0085] 2,4-dimethyldibenzoylmethane,

[0086] 2,5-dimethyldibenzoylmethane,

[0087] 4,4′-diisopropyldibenzoylmethane,

[0088] 4,4′-dimethoxydibenzoylmethane,

[0089] 4-tert-butyl-4′-methoxydibenzoylmethane,

[0090] 2-methyl-5-isopropyl-4′-methoxydibenzoyl methane,

[0091] 2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane,

[0092] 2,4-dimethyl-4′-methoxydibenzoylmethane,

[0093] 2,6-dimethyl-4-tert-butyl-4′-methoxydibenzoylmethane.

[0094] Preference is very particularly given according to the presentinvention, among the abovementioned dibenzoylmethane derivatives, to theuse of 4-tert-butyl-4′-methoxydibenzoylmethane, in particular thatoffered for sale under the trademark of “Parsol 1789” byHoffmann-LaRoche, this screening agent corresponding to the followingexpanded formula:

[0095] Another preferred dibenzoylmethane derivative according to thepresent invention is 4-isopropyldibenzoylmethane, a screening agent soldunder the name of “Eusolex 8020” by Merck and corresponding to thefollowing expanded formula (II):

[0096] The dibenzoylmethane derivative or derivatives are present in thecompositions in accordance with the invention at contents preferablyranging from 0.5 to 15% by weight and more preferably from 1% to 10% byweight and more particularly from 2 to 8% by weight, with respect to thetotal weight of the composition.

[0097] In addition, the compositions in accordance with the inventioncan comprise other additional, organic UV screening agents which areactive in the UV-A and/or UV-B regions (absorbers), the said screeningagents being water-soluble, fat-soluble or insoluble in commonly usedcosmetic solvents.

[0098] The additional organic UV screening agents are chosen inparticular from anthranilates; salicylic derivatives; cinnamicderivatives; camphor derivatives, other than thep-methylbenzylidenecamphor; triazine derivatives, such as thosedisclosed in U.S. Pat. No. 4,367,390, EP 863 145, EP 517 104, EP 570838, EP 796 851, EP 775 698, EP 878 469 and EP 933 376; benzophenonederivatives, other than those of formula (I); β,β-diphenylacrylatederivatives; benzotriazole derivatives; benzalmalonate derivatives;benzimidazole derivatives; imidazolines; p-aminobenzoic acid (PABA)derivatives; methylenebis(hydroxyphenylbenzotriazole) derivatives asdisclosed in Applications U.S. Pat. No. 5,237,071, U.S. Pat. No.5,166,355, GB 2 303 549, DE 197 26 184 and EP 893 119; screeningpolymers and screening silicones, such as those disclosed in particularin Application WO 93/04665; dimers derived from α-alkylstyrene, such asthose disclosed in Patent Application DE 198 55 649; and4,4-diarylbutadienes as disclosed in Applications EP 0 967 200, DE 19746 654, DE 197 55 649 and EP-A-1 008 586.

[0099] Mention may be made, as examples of additional organic screeningagents, of, denoted below under their INCI names:

[0100] para-Aminobenzoic Acid Derivatives:

[0101] PABA,

[0102] Ethyl PABA,

[0103] Ethyl Dihydroxypropyl PABA,

[0104] Ethylhexyl Dimethyl PABA, sold in particular under the name“Escalol 507” by ISP,

[0105] Glyceryl PABA,

[0106] PEG-25 PABA, sold under the name “Uvinul P25” by BASF,

[0107] Salicylic Derivatives:

[0108] Homosalate, sold under the name “Eusolex HMS” by Rona/EMIndustries,

[0109] Ethylhexyl Salicylate, sold under the name “Neo Heliopan TS” byHaarmann and Reimer,

[0110] Dipropyleneglycol Salicylate, sold under the name “Dipsal” byScher,

[0111] TEA Salicylate, sold under the name “Neo Heliopan TS” by Haarmannand Reimer,

[0112] Cinnamic Derivatives:

[0113] Ethylhexyl Methoxycinnamate, sold in particular under thetrademark “Parsol MCX” by Hoffmann-LaRoche,

[0114] Isopropyl Methoxy cinnamate,

[0115] Isoamyl Methoxy cinnamate, sold under the trademark “Neo HeliopanE 1000” by Haarmann and Reimer,

[0116] Cinoxate,

[0117] DEA Methoxycinnamate,

[0118] Diisopropyl Methylcinnamate,

[0119] Glyceryl Ethylhexanoate Dimethoxycinnamate,

[0120] β,β-Diphenylacrylate derivatives:

[0121] Octocrylene, sold in particular under the trademark “Uvinul N539”by BASF,

[0122] Etocrylene, sold in particular under the trademark “Uvinul N35”by BASF,

[0123] Benzophenone Derivatives:

[0124] Benzophenone-1, sold under the trademark “Uvinul 400” by BASF,

[0125] Benzophenone-2, sold under the trademark “Uvinul D50” by BASF,

[0126] Benzophenone-3 or Oxybenzone, sold under the trademark “UvinulM40” by BASF,

[0127] Benzophenone-4, sold under the trademark “Uvinul MS40” by BASF,

[0128] Benzophenone-5,

[0129] Benzophenone-6, sold under the trademark “Helisorb 11” byNorquay,

[0130] Benzophenone-8, sold under the trademark “Spectra-Sorb UV-24” byAmerican Cyanamid,

[0131] Benzophenone-9, sold under the trademark “Uvinul DS-49” by BASF,

[0132] Benzophenone-12,

[0133] Benzylidenecamphor Derivatives:

[0134] 3-Benzylidene camphor, manufactured under the name “Mexoryl SD”by Chimex,

[0135] Benzylidene Camphor Sulfonic Acid, manufactured under the name“Mexoryl SL” by Chimex,

[0136] Camphor Benzalkonium Methosulfate, manufactured under the name“Mexoryl SO” by Chimex,

[0137] Terephthalyidene Dicamphor Sulfonic Acid, manufactured under thename “Mexoryl SX” by Chimex,

[0138] Polyacrylamidomethyl Benzylidene Camphor, manufactured under thename “Mexoryl SW” by Chimex,

[0139] Phenylbenzimidazole Derivatives:

[0140] Phenylbenzimidazole Sulfonic Acid, sold in particular under thetrademark “Eusolex 232” by Merck,

[0141] Disodium Phenyl Dibenzimidazole Tetrasulfonate, sold under thetrademark “Neo Heliopan AP” by Haarmann and Reimer,

[0142] Triazine Derivatives:

[0143] Anisotriazine, sold under the trademark “Tinosorb S” by CibaSpecialty Chemicals,

[0144] Ethylhexyl triazone, sold in particular under the trademark“Uvinul T150” by BASF,

[0145] Diethylhexyl Butamido Triazone, sold under the trademark “UvasorbHEB” by Sigma 3V,

[0146] 2,4,6-tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine,

[0147] Phenylbenzotriazole Derivatives:

[0148] Drometrizole Trisiloxane, sold under the name “Silatrizole” byRhodia Chimie,

[0149] Methylenebis(benzotriazolyltetramethylbutyl-phenol), sold in thesolid form under the trademark “Mixxim BB/100” by Fairmount Chemical orin the micronized form in aqueous dispersion under the trademark“Tinosorb M” by Ciba Specialty Chemicals,

[0150] Anthranilic Derivatives:

[0151] Menthyl anthranilate, sold under the trademark “Neo Heliopan MA”by Haarmann and Reimer,

[0152] Imidazoline Derivatives:

[0153] Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate,

[0154] Benzalmalonate Derivatives:

[0155] Polyorganosiloxane comprising a benzalmalonate functional group,sold under the trademark “Parsol SLX” by Hoffmann-LaRoche,

[0156] 4,4-diarylbutadiene Derivatives:

[0157] 1,1-dicarboxy (2,2′-diméthyl-propyl)-4,4-diphénylbutadiène andtheir mixtures.

[0158] The organic UV screening agents which are more particularlypreferred are chosen from the following compounds:

[0159] Ethylhexyl Salicylate,

[0160] Ethylhexyl Methoxycinnamate,

[0161] Octocrylene,

[0162] Phenylbenzimidazole Sulfonic Acid,

[0163] Terephthalyidene Dicamphor Sulfonic Acid

[0164] Benzophenone-3,

[0165] Benzophenone-4,

[0166] Benzophenone-5,

[0167] 4-Methylbenzylidene camphor,

[0168] Disodium Phenyl Dibenzimidazole Tetrasulfonate,

[0169] Anisotriazine,

[0170] Ethylhexyl triazone,

[0171] Diethylhexyl Butamido Triazone,

[0172] 2,4,6-Tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine,

[0173] Methylenebis(benzotriazolyltetramethylbutyl-phenol),

[0174] Drometrizole Trisiloxane,

[0175] 1,1-dicarboxy (2,2′-diméthyl-propyl)-4,4-diphénylbutadiène, andtheir mixtures.

[0176] The cosmetic compositions according to the invention can alsocomprise pigments or alternatively nanopigments (mean size of theprimary particles: generally between 5 nm and 100 nm, preferably between10 nm and 50 nm) formed from coated or uncoated metal oxides, such as,for example, nanopigments formed from titanium oxide (amorphous orcrystallized in the rutile and/or anatase form), iron oxide, zinc oxide,zirconium oxide or cerium oxide, which are all UV photoprotective agentswell known per se. Conventional coating agents are, furthermore, aluminaand/or aluminum stearate. Such coated or uncoated metal oxidenanopigments are disclosed in particular in Patent Applications EP-A-0518 772 and EP-A-0 518 773.

[0177] The compositions according to the invention can also compriseagents for the artificial tanning and/or browning of the skin(self-tanning agents), such as, for example, dihydroxyacetone (DHA).

[0178] The compositions of the invention can additionally compriseconventional cosmetic adjuvants chosen in particular from fattysubstances, organic solvents, ionic or nonionic thickeners, softeners,antioxidants, agents for combating free radicals, opacifiers,stabilizers, emollients, silicones, α-hydroxy acids, antifoaming agents,moisturizing agents, vitamins, insect repellents, fragrances,preservatives, surfactants, anti-inflammatories, substance Pantagonists, fillers, polymers, propellants, basifying or acidifyingagents, colorants or any other ingredient commonly used in cosmetics, inparticular for the manufacture of antisun compositions in the form ofemulsions.

[0179] The fatty substances can be composed of an oil or a wax or theirmixtures. The term “oil” is understood to mean a compound which isliquid at ambient temperature. The term “wax” is understood to mean acompound which is solid or substantially solid at ambient temperatureand for which the melting point is generally greater than 35° C. Theyalso comprise fatty acids, fatty alcohols and esters of fatty acidswhich are linear or cyclic, such as derivatives of benzoic acid,trimellitic acid and hydroxybenzoic acid.

[0180] Mention may be made, as oils, of mineral oils (liquid paraffin);vegetable oils (sweet almond, macadamia, blackcurrant seed or jojobaoil); synthetic oils, such as perhydrosqualene, fatty alcohols, acids oresters (such as the C₁₂-C₁₅ alkyl benzoate sold under the trademark“Finsolv TN” by Finetex, octyl palmitate, isopropyl lanolate ortriglycerides, including those of capric/caprylic acids), oroxyethylenated or oxypropylenated fatty esters and ethers; silicone oils(cyclomethicone, polydimethylsiloxanes or PDMS); fluorinated oils; orpolyalkylenes.

[0181] Mention may be made, as waxy compounds, of paraffin wax, carnaubawax, beeswax or hydrogenated castor oil.

[0182] Mention may be made, among organic solvents, of lower alcoholsand polyols.

[0183] Of course, a person skilled in the art will take care to choosethis or these optional additional compounds and/or their amounts so thatthe advantageous properties, in particular the photostability,intrinsically attached to the compositions in accordance with theinvention are not, or not substantially, detrimentally affected by theenvisaged addition or additions.

[0184] The compositions of the invention can be prepared according totechniques well known to a person skilled in the art, in particularthose intended for the preparation of emulsions of oil-in-water orwater-in-oil type.

[0185] These compositions can be provided in particular in the form of asimple or complex emulsion (O/W, W/O, O/W/O or W/O/W), such as a cream,a milk, a gel or a cream gel, of a powder or of a solid tube and canoptionally be packaged as an aerosol and provided in the form of a foamor spray.

[0186] When it is a question of an emulsion, the aqueous phase of thelatter can comprise a nonionic vesicular dispersion prepared accordingto known processes (Bangham, Standish and Watkins, J. Mol. Biol., 13,238 (1965), FR 2 315 991 and FR 2 416 008).

[0187] The cosmetic composition of the invention can be used as acomposition for protecting the human epidermis or the hair againstultraviolet rays, as an antisun composition or as a make-up product.

[0188] When the cosmetic composition according to the invention is usedfor the protection of the human epidermis against UV rays or as anantisun composition, it can be provided in the form of a suspension ordispersion in solvents or fatty substances, in the form of a nonionicvesicular dispersion or in the form of an emulsion, preferably ofoil-in-water type, such as a cream or a milk, in the form of anointment, gel, cream gel, solid tube, powder, stick, aerosol foam orspray.

[0189] When the cosmetic composition according to the invention is usedfor the protection of the hair against UV rays, it can be provided inthe form of a shampoo, lotion, gel, emulsion or nonionic vesiculardispersion and can constitute, for example, a rinse-out composition, tobe applied before or after shampooing, before or after dyeing orbleaching, and before, during or after perming or hair straightening, astyling or treating lotion or a styling or treating gel, a lotion or agel for blow-drying or hair setting, or a composition for perming orstraightening, dyeing or bleaching the hair.

[0190] When the composition is used as a product for making up theeyelashes, eyebrows or skin, such as a treatment cream for theepidermis, foundation, lipstick tube, eyeshadow, face powder, mascara oreyeliner, it can be provided in the anhydrous or aqueous, pasty or solidform, such as oil-in-water or water-in-oil emulsions, nonionic vesiculardispersions, or suspensions.

[0191] By way of indication, for the antisun formulations in accordancewith the invention which exhibit a vehicle of oil-in-water emulsiontype, the aqueous phase (comprising in particular the hydrophilicscreening agents) generally represents from 50 to 95% by weight,preferably from 70 to 90% by weight, with respect to the entireformulation, the oily phase (comprising in particular the lipophilicscreening agents) from 5 to 50% by weight, preferably from 10 to 30% byweight, with respect to the entire formulation, and the(co)emulsifier(s) from 0.5 to 20% by weight, preferably from 2 to 10% byweight, with respect to the entire formulation.

[0192] As indicated at the beginning of the description, asubject-matter of the invention is the use of a composition as definedabove in the manufacture of a cosmetic of dermatological compositionintended for the protection of the skin and/or hair against ultravioletradiation, in particular solar radiation.

[0193] Another subject-matter of the present invention is a process forimproving the stability of at least one dibenzoylmethane derivative withrespect to UV radiation which consists in combining, with the saiddibenzoylmethane derivative, an effective amount of at least oneamino-substituted 2-hydroxybenzophenone derivative as defined above.

[0194] Another subject-matter of the present invention consists of theuse of an amino-substituted 2-hydroxybenzophenone derivative of formula(I) as defined above in the preparation of a cosmetic or dermatologicalcomposition comprising at least one UV screening agent of thedibenzoylmethane derivative type for the purpose of improving stabilitywith respect to UV radiation of the said dibenzoylmethane derivative.

[0195] Concrete but in no way limiting examples illustrating theinvention will now be given.

EXAMPLE 1

[0196] 80/20 Mixture of cetearyl alcohol and of oxyethylenated (33 EO)cetearyl alcohol (Sinnowax AO, Henkel) 7 g Mixture of glycerol mono- anddistearate 2 g (Cerasynt SD-V, ISP) Cetyl alcohol 1.5 gPolydimethylsiloxane (Dow Corning 200 Fluid, 1 g Dow Corning) C₁₂-C₁₅Alkyl benzoate (Witconol TN, Witco) 15 g n-Hexyl2-(4-diethylamino-2-hydroxybenzoyl)-benzoate 2 g ButylMethoxydibenzoylmethane (Parsol 1789, Hoffmann-LaRoche) 1.5 g Glycerol10 g Preservatives q.s. Demineralized water q.s. for 100 g

EXAMPLE 2

[0197] Glycerol mono/distearate/polyethylene glycol 2 g (100 EO)stearate mixture (Arlacel 165 FL, ICI) Stearyl alcohol (Lanette 18,Henkel) 1 g Palm oil stearic acid (Stéarine TP, Stéarinerie Dubois) 2.5g Polydimethylsiloxane (Dow Corning 200 Fluid, 0.5 g Dow Corning)C₁₂/C₁₅ Alkyl benzoate (Witconol TN, Witco) 15 g Triethanolamine 0.5 gn-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate 1.5 g ButylMethoxydibenzoylmethane 1 g (Parsol 1789, Hoffmann-LaRoche) Glycerol 5 gHexadecyl phosphate, potassium salt 1 g (Amphisol K, Hoffmann-LaRoche)Polyacrylic acid (Synthalen K, 3V) 0.3 g Hydroxypropyl methyl cellulose0.1 g (Methocel F4M, Dow Chemical) Triethanolamine q.s. pH 7Preservatives q.s. Demineralized water q.s. for 100 g

[0198] Each patent, patent application and literature article/reportcited or indicated herein is hereby expressly incorporated by reference.

[0199] While the invention has been described in terms of variousspecific and preferred embodiments, the skilled artisan will appreciatethat various modifications, substitutions, omissions, and changes may bemade without departing from the spirit thereof. Accordingly, it isintended that the scope of the present invention be limited solely bythe scope of the following claims, including equivalents thereof.

What is claimed is:
 1. A topically applicable cosmetic/dermatologicalsunscreen composition suited for the UV-photoprotection of human skinand/or hair, devoid of any p-methylbenzylidenecamphor, comprising (a) aneffective photoprotecting amount of at least one UV-screeningdibenzoylmethane compound, and (b) an effective photostabilizing amountof at least on UV-screening amino-substituted 2-hydroxybenzophenonecompound having the following structural formula (I):

in which R¹ and R², which may be identical or different, are each ahydrogen atom, a C₁-C₂₀ alkyl radical, a C₂-C₁₀ alkenyl radical, aC₃-C₁₀ cycloalkyl radical or a C₃-C₁₀ cycloalkenyl radical, with theproviso that R¹ and R² can together form, with the nitrogen atom towhich they are bonded, a 5- or 6-membered heterocyclic ring member; R³and R⁴, which may be identical or different, are each a C₁-C₂₀ alkylradical, a C₂-C₁₀ alkenyl radical, a C₃-C₁₀ cycloalkyl radical, a C₃-C₁₀cycloalkenyl radical, a C₁-C₁₂ alkoxy radical, a (C₁-C₂₀)alkoxycarbonylradical, a C₁-C₁₂ alkylamino radical, a di(C₁-C₁₂)alkylamino radical, anaryl radical or a heteroaryl radical which is optionally substituted, ora water-solubilizing substituent selected from among a carboxylategroup, a sulfonate group or an ammonium residue; X′ is a hydrogen atomor a —COOR⁵ or —CONR⁶R⁷ radical; R⁵, R⁶ and R⁷, which may be identicalor different, are each a hydrogen atom, a C₁-C₂₀ alkyl radical, a C₂-C₁₀alkenyl radical, a C₃-C₁₀ cycloalkyl radical, a C₃-C₁₀ cycloalkenylradical, a —(Y′O)₀-Z′ radical or an aryl radical; Y′ is —(CH₂)₂—,—(CH₂)₃—, -(CH₂)₄- or —CH -(CH₃)-CH₂—; Z′ is —CH₂—CH₃, —CH₂CH₂CH₃,—CH₂—CH₂—CH₂—CH₃ or —CH(CH₃)-CH₃; m′ is an integer ranging from 0 to 3;n′ is an integer ranging from o to 3; and o is an integer ranging from 1to 2, formulated into (c) a topically applicable,cosmetically/dermatologically acceptable vehicle, diluent or carriertherefor.
 2. The cosmetic/dermatological sunscreen composition asdefined by claim 1, wherein the ratio by weight of the at least oneamino-substituted 2-hydroxybenzophenone compound of formula (I) to theat least one dibenzoylmethane compound is greater than
 1. 3. Thecosmetic/dermatological sunscreen composition as defined by claim 1,said at least one compound of formula (I) comprising those of thefollowing formula (Ia):

in which R¹ and R², which may be identical or different, are each ahydrogen atom, or a C₁-C₁₂ alkyl radical or together form, with thenitrogen atom to which they are bonded, a 5- or 6-membered heterocyclicring member; X is COOR⁵ or CONR⁶R⁷; R⁵ is a hydrogen atom, a C₁-C₁₂alkyl radical or a C₃-C₆ cycloalkyl radical; R⁶ and R⁷, which may beidentical or different, denote a hydrogen atom, a C₁-C¹² alkyl radicalor a C₅-C₆ cycloalkyl radical.
 4. The cosmetic/dermatological sunscreencomposition as defined by claim 3, wherein fomula (Ia), R¹ and R², whichmay be identical or different, are each a C₁-C₄ alkyl radical; R⁵ is aC₃-C₈ alkyl radical; and R⁶ and R⁷, which may be identical or different,denote a C₁-C₈ alkyl radical.
 5. The cosmetic/dermatological sunscreencomposition as defined by claim 1, said at least one compound of formula(I) comprising those of the following formula (Ib):

in which R¹ and R², which may be identical or different, are each aC₁-C₁₂ alkyl radical, or together form, with the nitrogen atom to whichthey are bonded, a 5- or 6-membered heterocyclic ring member.
 6. Thecosmetic/dermatological sunscreen composition as defined by claim 5,said at least one compound of formula (Ib) comprising4-diethylamino-2-hydroxyphenyl phenyl ketone and/or4-pyrrolidino-2-hydroxyphenyl phenyl ketone.
 7. Thecosmetic/dermatological sunscreen composition as defined by claim 1,said at least one compound of formula (I) comprising those of thefollowing formula (Ic):

in which R¹ and R², which may be identical or different, are each denotea hydrogen atom, or a C₁-C₈ alkyl radical, or together form, with thenitrogen atom to which they are bonded, a 5- or 6-membered heterocyclicring member; and R⁵ is a hydrogen atom, a C₁-C₁₂ alkyl radical or aC₃-C₆ cycloalkyl radical.
 8. The cosmetic/dermatological sunscreencomposition as defined by claim 7, said at least one compound of formula(Ic) comprising 2-(4-pyrrolidino-2-hydroxybenzoyl)benzoic acid, methyl2-(4-diethylamino-2-hydroxybenzoyl)benzoate, 2-ethylhexyl2-(4-diethylamino-2-hydroxybenzoyl)-benzoate, cyclohexyl2-(4-diethylamino-2-hydroxybenzoyl)-benzoate, n-hexyl2-(4-diethylamino-2-hydroxybenzoyl)benzoate,2-(4-dibutylamino-2-hydroxybenzoyl)benzoic acid, methyl2-(4-dibutylamino-2-hydroxybenzoyl)benzoate, and/or isobutyl2-(4-dibutylamino-2-hydroxybenzoyl)benzoate.
 9. Thecosmetic/dermatological sunscreen composition as defined by claim 8,said at least one compound of formula (Ic) comprising n-hexyl2-(4-diethylamino-2-hydroxybenzoyl)benzoate.
 10. Thecosmetic/dermatological sunscreen composition as defined by claim 1, inwhich the said at least one amino-substituted 2-hydroxybenzophenonecompound of formula (I) comprising from 0.1 to 15 by weight, withrespect to the total weight thereof.
 11. The cosmetic/dermatologicalsunscreen composition as defined by claim 10, said at least oneamino-substituted 2-hydroxybenzophenone compound of formula (I)comprising from 1 to 10% by weight, with respect to the total weightthereof.
 12. The cosmetic/dermatological sunscreen composition asdefined by claim 11, said at least one amino-substituted2-hydroxybenzophenone compound of formula (I) comprising from 2 to 8% byweight, with respect to the total weight thereof.
 13. Thecosmetic/dermatological sunscreen composition as defined by claim 1,said at least one dibenzoylmethane compound comprising from 0.5% to 15%by weight, with respect to the total weight thereof.
 14. Thecosmetic/dermatological sunscreen composition as defined by claim 13,said at least one dibenzoylmethane compound comprising from 1% to 10% byweight, with respect to the total weight thereof.
 15. Thecosmetic/dermatological sunscreen composition as defined by claim 14,said at least one dibenzoylmethane compound comprising from 2% to 8% byweight, with respect to the total weight thereof.
 16. Thecosmetic/dermatological sunscreen composition as defined by claim 1,additionally comprising at least one other organic screening agent whichis active in the UV-A and/or UV-B regions.
 17. Thecosmetic/dermatological sunscreen composition as defined by claim 16,said additional organic UV screening agent or agents being selected fromamong anthranilates; cinnamic derivatives; salicylic derivatives;camphor derivatives, other than p-methylbenzylidenecamphor; triazinederivatives; benzophenone derivatives, other than those of formula (I);β,β-diphenylacrylate derivatives; benzotriazole derivatives;benzalmalonate derivatives; benzimidazole derivatives; imidazolines;bisbenzoazolyl derivatives; p-aminobenzoic acid (PABA) derivatives;methylenebis(hydroxyphenylbenzotriazole) derivatives; screening polymersand screening silicones; dimers derived from α-alkylstyrene; and4,4-diarylbutadienes.
 18. The cosmetic/dermatological sunscreencomposition as defined by claim 17, said organic UV screening agent oragents being selected from among Ethylhexyl Salicylate, Octocrylene,Ethylhexyl Methoxycinnamate, Phenylbenzimidazole Sulfonic Acid,Benzophenone-3, Benzophenone-4, Benzophenone-5, 4-Methylbenzylidenecamphor, Disodium Phenyl Dibenzimidazole Tetrasulfonate, Anisotriazine,Ethylhexyl triazone, Diethylhexyl Butamido Triazone,2,4,6-Tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine, DrometrizoleTrisiloxane, Methylenebis(benzotriazolyltetramethylbutyl-phenol),1,1-dicarboxy(2,2′-dimethylpropyl)-4,4-dipenylbutadiene, and mixturesthereof.
 19. The cosmetic/dermatological sunscreen composition asdefined by claim 1, additionally comprising coated or uncoated metaloxide pigments or nanopigments.
 20. The cosmetic/dermatologicalsunscreen composition as defined by claim 19, said pigments ornanopigments comprising coated or uncoated titanium dioxide, zinc oxide,iron oxide, zirconium oxide or cerium oxide, and mixtures thereof. 21.The cosmetic/dermatological sunscreen composition as defined by claim 1,additionally comprising at least one agent for the artificial tanningand/or browning of the skin.
 22. The cosmetic/dermatological sunscreencomposition as defined by claim 1, additionally comprising at least oneadjuvant or additive selected from among fatty substances, organicsolvents, ionic or nonionic thickeners, softeners, antioxidants, agentsfor combating free radicals, opacifiers, stabilizers, emollients,silicones, α-hydroxy acids, antifoaming agents, moisturizing agents,vitamins, insect repellents, fragrances, preservatives, surfactants,anti-inflammatories, substance P antagonists, fillers, polymers,propellants, basifying or acidifying agents, or colorants.
 23. Thecosmetic/dermatological sunscreen composition as defined by claim 1,formulated as a nonionic vesicular dispersion, an O/W or W/O emulsion, acream, a milk, a gel, a cream gel, a suspension, a dispersion, a powder,a solid tube, a foam or a spray.
 24. The cosmetic/dermatologicalsunscreen composition as defined by claim 1, formulated as a makeup forthe eyelashes, eyebrows or skin and provided in the anhydrous oraqueous, pasty or solid form, in the form of an emulsion, of asuspension or of a dispersion.
 25. The cosmetic/dermatological sunscreencomposition as defined by claim 1, formulated for the protection of thehair against ultraviolet rays and provided in the form of a shampoo, ofa lotion, of a gel, of an emulsion, or of a nonionic vesiculardispersion.
 26. A regime or regimen for photoprotecting human skinand/or hair against the deleterious effects of ultraviolet irradiation,comprising topically applying thereon an effective amount of acosmetic/dermatological sunscreen composition that does not contain anyp-methylbenzylidenecamphor, but which comprises (a) an effectivephotoprotecting amount of at least one UV-screening dibenzoylmethanecompound, and (b) an effective photostabilizing amount of at least oneUV-screening amino-substituted 2-hydroxybenzophenone compound having thefollowing structural formula (I):

in which R¹ and R², which may be identical or different, are each ahydrogen atom, a C₁-C₂₀ alkyl radical, a C₂-C₁₀ alkenyl radical, aC₃-C₁₀ cycloalkyl radical or a C₃-C₁₀ cycloalkenyl radical, with theproviso that R¹ and R² can together form, with the nitrogen atom towhich they are bonded, a 5- or 6-membered heterocyclic ring member; R³and R⁴, which may be identical or different, are each a C₁-C₂₀ alkylradical, a C₂-C₁₀ alkenyl radical, a C₃-C₁₀ cycloalkyl radical, a C₃-C₁₀cycloalkenyl radical, a C₁-C₁₂ alkoxy radical, a (C₁-C₂₀)alkoxycarbonylradical, a C₁-C₁₂ alkylamino radical, a di(C₁-C₁₂)alkylamino radical, anaryl radical or a heteroaryl radical which is optionally substituted, ora water-solubilizing substituent selected from among a carboxylategroup, a sulfonate group or an ammonium residue; X′ is a hydrogen atomor a —COOR⁵ or —CONR⁶R⁷ radical; R⁵, R⁶ and R⁷, which may be identicalor different, are each a hydrogen atom, a C₁-C₂₀ alkyl radical, a C₂-C₁₀alkenyl radical, a C₃-C₁₀ cycloalkyl radical, a C₃-C cycloalkenylradical, a —(Y′O)₀-Z′ radical or an aryl radical; Y′ is —(CH₂)₂—,—(CH₂)₃—, -(CH₂)₄- or —CH-(CH₃)-CH₂-; Z′ is —CH₂—CH₃, —CH₂CH₂CH₃,—CH₂—CH₂—CH₂—CH₃ or —CH(CH₃)-CH₃; m′ is an integer ranging from 0 to 3;n′ is an integer ranging from 0 to 3; and o is an integer ranging from 1to 2, formulated into (c) a topically applicable,cosmetically/dermatologically acceptable vehicle, diluent or carriertherefor.
 27. A method for photostabilizing at least one UV-screeningdibenzoylmethane compound in the absence of anyp-methylbenzylidenecamphor, comprising formulating therewith aneffective stabilizing amount of at least one amino-substituted2-hydroxybenzophenone compound as defined in claim 1.